Novel compositions and photographic processes

ABSTRACT

Novel adducts are formed from a thioamine and glutaraldehyde. The adducts when incorporated in photographic processing compositions increase the efficiency of development of exposed silver salts.

United States Patent 11 1 1111 3,869,289

Amering 1 Mar. 4, 1975 [54] NOVEL COMPOSITIONS AND [56] References CitedPHOTOGRAPHIC PROCESSES UNITED STATES PATENTS [75] Inventor: Charles F.Amering, Rochester, 3,282,694 11/1966 'Luckey 96/61 y 3,615,488 10/1971Drago 96/66 R 73 A E t K d k C 3,615,513 10/1971 Haist 96/61 M l 1 1133?OTHER PUBLICATIONS Filed. Feb 15 1973 Ratner et a1., J A.C.S. 59,200(1937). [211 Appl. No.: 332,964 Primary Examiner-M. F. Kelley RelatedU 8 Application Data Attorney, Agent, or FirmH. E. Byers [62] Divisionof Ser. No. 104,690, Jan. 7, 1971. [57] ABSTRACT Novel adducts areformed from a thioamine and glu- 'i taraldehyde. The adducts whenincorporated in photo- [58] Fie'ld M 50 PT graphic processingcompositions increase the effi- 96/1 1 ciency of development of exposedsilver salts.

10 Claims, 2 Drawing Figures DENSITY 1x Us PATENTED 41975 sum 1 [I 2 L06EXPOSURE CHARL 55 F. AMER/N6 INVENTOR.

BY /W A T TORNE Y PATENIEQ HAR 4197.5

sum a {I 2 LOG EXPOSURE FIG. 2

CHARLES E AMER/N6 INVENTOR.

ATTORNEY 1 NOVEL COMPOSITIONS AND PHOTOGRAPI-IIC PROCESSES This is adivision of U.S. Patent Application Ser. No. 104,690, filed Jan. 7,1971.

BACKGROUND OF THE INVENTION 1. Field of the Invention This inventionrelates to new compositions of matter, process of preparing suchcompositions, photographic processing compositions containing the novelcompositions and to processes employing said processing compositions. Inone aspect, this invention relates to a new composition of matter whichis an adduct of a thioamine and glutaraldehyde. In another aspect, thisinvention relates to the methods of preparing the novel adducts. In yetanother aspect, this invention relates to processes of developingexposed silver salts in a photographic element employing said processingcomposition.

2. Description of the Prior Art The processing of photographic materialshas for many years been performed by conventional processing methodssuch as tank and tray processing methods. The quality of theconventionally processed photographic material has generally beensatisfactory. However, the processing time is generally long, that is,in the order of from to minutes.

In recent years, the use of roller transport systems have come intovogue. Through the employment of such transport systems the time ofprocessing photographic elements has been reduced to minutes and oftenreduced to as short a time as below about a minutc.

In attempts to further increase the speed of existing machine processes,such as by raising processing and drying temperatures, there isgenerally obtained a product which suffers from a substantial reductionin the sensitometric properties of the film. It is evident, therefore,that the art would greatly benefit should there be discovered a means ofincreasing the photographic speed of films, with respect to theprocessing of said films, without any substantial detrimental affects onthe sensitometric properties such as, for example, a reduction incontrast or D,,,,,,. In the case of medical radiography, both anincrease of speed and an improvement in D and contrast would greatlyenhance the radiographic techniques as a diagnostic tool.

The increase in photographic speed with respect to development providesseveral degrees of freedom not ordinarily available, for example, onemay decrease the silver halide coverage, the processing time of theexposed film can be decreased or with regard to radiography, the patientmay be exposed to smaller amounts of radiation.

Although it is known to add either cysteine or aldehydes to photographicsystems, i.e., photographic elements and photographic processingcompositions, it has not been taught heretofore that one may incorporatethe novel adducts of this invention into a photographic processingcomposition.

SUMMARY OF THE INVENTION In accordance with this invention, there areprovided photographic processing compositions which exhibit a markedincrease in photographic speed accompanied by an improvement insensitometric properties such as D,,,,,, and contrast. The photographicprocessing compositions of this invention contain, in addition to thewell known ingredients, an adduct of a thioamine and glutaraldehyde. Asused hereinafter, thioamines include derivatives thereof.

It is accordingly an object of this invention to provide means forincreasing the photographic speed of electromagnetic radiation sensitiveelements.

It is another object to improve the sensitometric properties ofphotographic elements.

It is another object to provide a new composition of matter which is anadduct of an aminothiol and glutaraldehyde.

It is still another object to provide means for preparation of the noveladducts. It is another object to provide photographic processingcompositions containing the novel adducts.

Other objects of this invention will become obvious to those skilled inthe art from that which follows:

DESCRIPTIONOF THE PREFERRED EMBODIMENTS In accordance with thisinvention, the above and other objects are attained by providing anadduct of a thioamine or derivative thereof with glutaraldehyde. Thenovel adducts so provided are incorporated in photographic processingcompositions thereby significantly increasing the efficiency of thedevelopers in developingexposed silver salts. Thioamine should beunderstood to be an amine compound containing a sulfur atom having anoxidation state of two. Illustrative of the thioamines which mayadvantageously be utilized are aminothiols, aminodisulfides andthiolactones.

The first of said compounds or their salts, preferably the hydrochloridesalts, which are preferably employed in the formation of the adductsemployed in this invention fall into two general classes. Compoundsillustrative of Class I each contain at least one sulfur atom having anoxidation state of two, a carboxy group or its lactone, and an aminogroup. Compounds illustrative of Class I are cysteine or its homologuesand other amino acids containing a sulfur atom having an oxidation stateof two. Compounds of Class II contain an amino group, and a sulfur atomhaving an oxidation state of two. The following is an illustrativenon-limiting list of the first compound suitable in forming the adductsof this invention:

Class I L-eysteine I-ICI,

L-cystine,

DL-penicillamine, and

DL-homocysteinethiolactone HCl Class II Z-aminoethanethiol HCl In apreferred aspect of this invention, the compounds employed in formingthe adducts of this invention are those of Class I. In another preferredaspect cysteine, cystine, penicillamine, homocysteinethiolactone and2-aminoethanethiol.HCl are utilized in forming the adduct. In yetanother preferred aspect, cysteine is employed in forming the adduct.

The second of said compounds employed in the formation of the adductsemployed in this invention is glutaraldehyde.

Illustrative of the adducts which may be employed in this invention arethe products obtained by mixing: cysteine and glutaraldehyde,glutaraldehyde and DL- penicillamine, glutaraldehyde and DL-homocysteinethiolactone, glutaraldehyde and DL-methionine, glutaraldehyde and2-aminoethanethiol. Preferred adducts are those formed fromglutaraldehyde and one of L-eysteine.I-ICI, L-cystine, DL-penicillamine,DL- homocysteinethiolactone.HCl or 2-aminoethanethiol.I-ICl.

The adducts of this invention are easily prepared by merely addingglutaraldehyde to the thiamine or,vice VEISfluThE adduct can be formedin situ with respect to the processing composition or the adduct can bepreformed and then added to the developer solution. It is generally moredesirable to form the adduct first and then add it to the processingcomposition as compared to forming the adduct in situ with regard to theprocessing composition. The preferability of preforming the adduct ismanifested through the additional speed increase observed over thatobtained by in situ formation; however, the processing compositioncontaining the adduct formed in situ evidences substantial improvementsover the prior art. It should be understood, therefore, that theinvention includes both preformed adducts and adducts formed by addingthe compounds separately to the processing composition.

FIG. 1, which describes a characteristic H and D curve compares thedensity versus log exposure for emulsion processed in: a controldeveloper solution (I), the same control developer solution to whichglutaraldehyde has been added (2), the same control developer solutionto which cysteine has been added (3), and the developer solution towhich a preformed adduct has been added. A more detailed description ofFIG. 1 is found in Example 3.

FIG. 2 which shows the characteristic H and D curves of density versuslog exposure illustrates that both the processing solution (3)containing the preformed adduct and the processing solution (2) in whichthe adduct is formed in situ are superior to the processing solution (1)absent the adduct but otherwise identical. The processing solutioncontaining the adduct clearly showed increased speed and contrast asmanifested by the developed film as compared with the processingsolution absent the adduct.

The adduct when preformed can be prepared under acid, neutral, or basicconditions. The solvent employed can be any in which both the first andsecond compound are soluble. A preferred solvent is water.

The adducts of this invention have been subjected to a thoroughanalytical investigation, however, the structure and composition remainsindefinite. It is clear, however, that a novel composition is formed bythe reaction of the first and second compounds as exemplified by ExampleI. Table II, for example, illustrates the color changes over a period oftime said color changing manifesting that a new product is being formed.

The adduct is readily soluble in highly acid and basic solutions,however, as the pH of the solution is made to approach neutrality theadduct precipitates out. The adduct can be added to the processingsolution in any form, i.e., as a precipitate, as a basic solution or asan acid solution.

Some adduct is formed as soon as the two compounds are in contact,however, the longer the compounds are allowed to react the more adductis formed. After as short a time as two hours of reaction, the obtainedadduct substantially improved the photographic processing composition.After about 24 hours of reaction time, the adductobtained causes apotent increase 4 in photographic speed with regard to the processingcomposition.

The photographic speed increases obtained in processing photographicmaterials in the presence of the adducts vary in relation to the amountof first compound (thioamine) employed in forming the adduct as well asthe ratio of said first compound to said second compound(glutaraldehyde). Increases in the concentration of cysteine isaccompanied by speed increases. The useful ratios of first compound tosecond compound can vary over a wide range, said ranges being easilydetermined through routine experimentation. When, however, the adduct isemployed in photographic processing compositions, the first compoundshould not be present in substantial excess over the second compoundsince a serious reduction in speed may be produced. As a general rule,the adduct can comprise a molar ratio of from about 4 to l to about 1 to60 of said first compound to said second compound. A preferred molarratio is from about 2 to l to about 1 to 8 of said first compound tosaid second compound. Another preferred range is from I to 1 to about Ito 2 of said first compound to said second compound. Still anotherpreferred ratio is about a l to 1 ratio of said first and secondcompound.

The adducts are not reducing agents for silver salts and therefore aloneare not effective as photographic developing agents. It has beendiscovered, however, that when added to a photographic developing or processing composition, the developing activity of the composition isgreatly enhanced. Withoug being bound by any theoretical explanation, itwould appear that the adducts of this invention increase the efficiencyof the developing power of the developing or processing composition. v

The adducts of this invention extend broadly to all photographicdeveloper and processing compositions. However, the novel developing orprocessing solutions, i.e., those solutions.containing the noveladducts, are of greatest practical importance with respect to high speedmaterials such as radiographic materials, separation negative materialsand the like. The compositions, in addition to containing a developingagent and the novel adducts can contain other ingredients employed inthe processing of a photographic product, for example, stabilizercompositions, monobaths, activator compositions, hardener compositionsand the like. Preferably, the adducts are employed in an aqueousalkaline developer solution.

The adduct concentration in the processing solutions can vary over awide range. It has been discovered, however, that the sensitometricproperties such as D,,,,, and contrast as well as speed are improvedwith increasing concentration of the adduct. With each of the adductsthere is a point at which increased concentration, for example 0.30 g/lbased on said first compound, will produce an increase in fog, however,the increase in the fog level is readily counteracted through the use ofantifoggants. Typical processing and developing solutions contain fromabout 0.05 g/l to about 0.50 g/l. A preferred concentration is fromabout 0.12 g/l to about 0.24 g/l. A preferred concentration is 0.12 g/l.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, and from the drawings, of which FIGS. 1and 2 compares characteristic curves for processing compositions of thisinvention and for the prior art composition.

The following examples are included for a further understanding of theinvention.

EXAMPLE 1 A developer solution (C) is prepared as in (A) but modified bythe addition of 0.24 gram of cysteine.

Separate sheets of a coarse-grained silver bromoiodide negative materialof the type used in medical radi- This example illustrates a preferredmethod of pre- 5 ography is sensitometrically exposed and processed inparing the novel adducts of this invention. a roller type processor at95C employing one of the To an aqueous solution at a pH of 1.4 is added1 mole above developers. The results are summarized in Table L-eysteineand 1 mole of glutaraldehyde. .The solution is allowed to stand for 20hours. Upon mixing the solution remains clear and colorless. After about1 hour the TABLE I11 solution begins to turn straw in color andthereafter gradually turns to an amber color. The adduct is pre-Sensitometric Results cipitated out of solution by slowly raising the pHAdd d en through the addltton of pyrtdlne. l5 Cysteine. Reiative Adductsare slmilarly prepared by mixing glutaralde- Developer Concemmno" Fog pContrast DmflX hyde with cystme penlcillamtne, homocystelnethlolac- A(Control) '18 2'60 3A4 tone, serme, methionine. alanine, proline,3-mercapto- B 0.12 g/liter .18 1.30 2.68 3.52 propionic acid orZ-aminoethanethiol. The adducts C 034 l8 formed from Serme alanine,P1011116 and p 20 The above data illustrate that at least 307: speedincrease rcsultsfrom the presence propionic acid are di y f r however hotthc cystcinmwithout significantly lowering the contrast or Dmax asoften occurs with other speed increasing addenda. pear not to have asignificant affect on the photographic speed. The results with referenceto color and the pH are summarized in Table 11. EXAMPLE 3 AS Will beSeen in Table VI below Simllaf adducts This example illustrates theemployment of the novel ShOW no 1111111) and hence are not Wlti'lln theSCOPE Of processing composition containing the preformed adthisinvention. ducts.

TABLE 11 pH and Color at Compound. 1:1 M. with Glutaraldehyde Mixing 15Minutes 1 Hour 4 Hours 20 Hours 1=Cysteine.HCl 1.4 clear 1.4 clear 1.25straw 1.2 straw 1.2 amber *L-Cystine 1.5M Cystine: 1M (1A) 3.1 milky 3.2cloudv 3.25 cloudy 3.3 orange 3.3 orange DL-Penicillamine 3.6 clear 33straw 3.15 amber 3.15 amber 3.15 red L-Homocysteinethiolactone.HCI 1.5straw 1.3 amber 1.3 red 1.15 brown 1.15 black L Serine 4.4 clear 4.4clear 3.4 straw 3.5 straw 3.5 amber DLMethionine 4.3 stra 3.9 orange 3.)orange 3 9 orange 3.) tan pptd DL-Alanine 4.25 stravt 3.9 red 3.9 brown3 9 brown 3.85 black L-Proline 4.35 clear 4.35 clear 4.35 clear 4.35clear 4.35 clear 3 Mercaptopropionic Acid 2.2 clear 2.2 clear 2.2 clear2.2 clear 22 cloudy 2 AminoethanethioLHCl 2.35 clear 2.3 pale green 1.7yellow 1.5 yellow 1.5 amber insoluble in H- -O at the pH of mixingEXAMPLE 2 A series of four high speed silver bromoiodide photo- Thisexample illustrates that the adduct which may graphlc exposed andrespectwelY tray be formed in situ produces photographic speedinproceissed m typical hlgh Contrast photograph: decreases as a resultof the photographic development Velopmg Solution process.

Developer 1 Control Developer A developer solution (A) is prepared tocontain: lrPile"ylj3'llyrilmlld0nc L5 Hydroqumone 30.? g l p| r L5Potassium sulfite 45 percent aqueous 90.1 m ila m wg I one 30'0 gPotassium carbonate 10.0 g Potassium sulfite 45 percent aqueous 90.0 mlsN'tromdazole g Potassium carbonate 10.0 g h benzoinazole giNitroindazok 0.25 g Potasslum bromide 4.0 g 5-Methyl benzotriazole 0.06g E D T A 1 Potassium bromide 10.0 g. Water to p m 05 Sodium bisulfite3.75 Glutaraldehyde 25 percent aqueous 18.6 m Developer 2 Control g/l ofglutaraldehyde E D T A L0 g Developer 3 Control 0.12 g/l of l-cystemeHClI water to Developer 4 Control preformed adduct of cysteine pH 10.05 andglutaraldehyde *Ethylcnediamine 'l'etraacctic Acid A developer solution(B) is prepared as in (A). but modified by the addition of 0.12 gram ofcysteine.

The samples are fixed, washed and dried in the conventional manner. Theresults are summarized in FIG. 1 and Table IV.

TABLE IV Developer Rel. Speed at 0.85 Above Fog FIG. 1 shows thecharacteristic H and D curves of density versus log exposure for 25seconds development time for each of the four processing compositions.Based upon the control (line 1) adding glutaraldehyde alone (line 2)produces essentially no increase in speed. L-cysteine added to adeveloper without glutaraldehyde (line 3) produces only a slightincrease in speed. A substantial increase in speed and contrast isproduced as shown by line 4 when the preformed adduct of l-cysteine.HC1and glutaraldehyde are added to the control processing composition. Thisamounts to a doubling of the photographic speed due to the particulardeveloper solution.

EXAMPLE 4 This example illustrates that the concentration of the adductas measured by the amount of first compound employed in the preparationof the adduct affects the speed.

Seven samples of a high speed silver bromoiodide photographic emulsionare exposed and respectively tray processed in one of the processingsolutions as summarized in Table V. These represent various amounts andratios of cysteine and glutaraldehyde. The control solution is similarto the control in Example 3.

Several preformed adducts of glutaraldehyde and a compound listed inTable VI are prepared as in Example l. The adducts so prepared includethose of the invention and similarly formed compositions not within thescope of this invention.

Several high speed silver bromoiodide emulsions are exposed andprocessed in the control developer employed as in Example 3 or in thedeveloper which includes a preformed adduct. In each case, the adduct isformed from a 1 to 1 molar aqueous solution of first compound and secondcompound. The results are summarized in Table VI.

EXAMPLE 6 This example illustrates that the adducts which are useful inthis invention should be formed from a compound which contains both asulfur group and a nitrogen group such as aminoacids from proteinhydrolysates, cysteine and aminoethanethiols whereas adducts formed fromcompounds not containing both a nitrogen group and a sulfur group do notcontribute to a significant increase in the photographic speed. Thus,only minor increases are shown by the L-serine, DL methionine,DL-alamine, L-proline and 3-mercaptopropionic acid.

A speed increase during development in the presence of cysteineglutaraldehyde occurs with films sensitized to the infrared. Strips ofsuch films after exposure are developed in a developer comprising:

TABLE VI Conc. Millimole/l of adduct Development was at 68 for 8 minutesThe above solution is modified by the addition of 0.05 g cysteinehydrochloride and 0.05 g glutaraldehyde bisulfite. Exposed strips aredeveloped as above. Sensitometric curves are plotted for the two sets ofdeveloped infrared films. A 0.10 speed increase is obtained for filmsdeveloped in the developer containing the cysteine and theglutaraldehyde. The increase in speed also occurs over and above thenormal increase in speed which results from known hypering treatments,as, for example, treatment with aqueous ammonium at about 45 for 40seconds prior to exposure. In such cases, a total speed increase of 0.40may result.

The silver halide layers which can be processed with the processingcompositions of this invention can comprise silver chloride, silverbromide, silver bromoiodide, silver chlorobromoiodide or mixturesthereof. Suitable emulsions may be coarse or fine grain and can beprepared by any of the well-known procedures, e.g., single jetemulsions, double jet emulsions, such as Lippmann emulsions, ammonicalemulsions, thiocyanate or thioether ripened emulsions such as thosedescribed in Nietz et al. US. Pat. No. 2,222,264 issued Nov. 4, 1940;Illingsworth US. Pat. No. 3,320,069 issued May 15, 1967; and McBride US.Pat. No. 3,271,157 issued Sept. 6, 1966. Surface image emulsions maybe-used or internal image emulsions such as those described in Davey etal. US. Pat. No. 2,592,250 issued Apr. 8, 1952; Porter et al. US. Pat.No. 3,206,313 issued Sept. 14, 1965; Berriman US. Pat. No. 3,367,778issued Feb. 6, 1968 and Bacon et al. US. Pat. No. 3,447,927 issued June3, 1969. If desired, mixtures of surface and internal image emulsionsmay be used as described in Luckey et al.'U.S. Pat. No. 2,996,382 issuedApr. 15,

1961. Negative type emulsions may be used or direct positive emulsionssuch as those described in Leermakers U.S. Pat. No. 2,184,013 issuedDec. 19, 1939; Kendall et al. U.S. Pat. No. 2,541,472 issued Feb. 13,1951; Berriman U.S. Pat. No. 3,367,778 issued Feb. 6, 1968; SchouwenaarsBritish Pat. No. 723,019; lllingsworth et al. French Pat. No. 1,520,821;Ives U.S. Pat. No. 2,563,785 issued Aug. 7, 1951; Knott et al. U.S. Pat.No. 2,456,953 issued Dec. 21, 1968 and Land U.S. Pat. No. 2,861,885issued Nov. 25, 1958. The emulsions may be regular grain emulsions suchas the type described in Klein and Moisar, J. Phat. Sci., Vol. 12, No.5, Sept./Oct., 1964, pp 242-251.

The emulsions which are processed with the processing solutions of thisinvention may be sensitized with chemical sensitizers, such as withreducing agents; sulfur, selenium or tellurium compounds; gold, platinumor palladium compounds; or combinations of these. Suitable proceduresare described in Sheppard et al. U.S. PatfNo. 1,623,499 issued Apr. 5,1927; Waller et al. U.S. Pat. No. 2,399,083 issued Apr. 23, 1946; Me-Veigh U.S. Pat. No. 3,297,447 issued Jan. 10, 1967; and Dunn U.S. Pat.No. 3,297,446 issued Jan. 10, 1967.

The silver halide emulsions or layers which can be processed with theprocessing solutions of this invention may contain speed increasingcompounds such as polyalkylene glycols, cationic surface active agentsand thioethers or combinations of these as described in Piper U.S. Pat.No. 2,886,437 issued May 12, 1959; Dann et al. U.S. Pat. No. 3,046,134issued July 24, 1962; Carroll et al. U.S. Pat. No. 2,944,900 issued July12, 1960; and Goffe U.S. Pat. No. 3,294,540 issued Dec. 27, 1966.

The silver halide emulsions or layers which can be processed with theprocessing solutions of this invention can be protected against theproduction of fog and can be stabilized against loss of sensitivityduring keeping. Suitable antifoggants and stabilizers eachused alone orin combination include thiazolium salts described in Brooker et al. U.S.Pat. No. 2,131,038 issued Sept. 27, 1938 and Allen et al. U.S. Pat. No.2,694,716 issued Nov. 16, 1954; the azaindenes described in Piper U.S.Pat. No. 2,886,437 issued May 12, 1959 and Heimbach et al. U.S. Pat. No.2,444,605 issued July 6, 1948; the mercury salts as described in Allenetal. U.S. Pat. No. 2,728,663 issued Dec. 27, 1955; the urazolesdescribed in Anderson et al. U.S. Pat. No. 3,287,135 issued Nov. 22,1966; the sulfocatechols described in Kennard et al. U.S. Pat. No.3,236,652 issued Feb. 22, 1966; the oximes described in Carroll et al.British Pat. No. 623,448; nitron; nitroindazoles; the mercaptotetrazolesdescribed in Kendall et al U.S. Pat. No. 2,403,927 issued July 16, 1946;Kennard et al. U.S. Pat. No. 3,266,897 issued Aug. 16, 1966 and Luckeyet al. U.S. Pat. No. 3,397,987 issued Aug. 20, 1968; the polyvalentmetal salts described in Jones U.S. Pat. No. 2,839,405 issued June 17,1958; the thiuronium salts described in Herz et al. U.S. Pat. No.3,220,839 issued Nov. 30, 1965; the palladium, platinum and gold saltsdescribed in Trivelli et al. U.S. Pat. No. 2,566,263 issued Aug. 28,1951 and Yutzy et al. U.S. Pat. No. 2,597,915 issued May 27, 1952.

The photographic elements which are processed with the processingsolutions of this invention may contain in place of or in combinationwith the developing agents present in the processing solution,incorporated developing agents such as hydroquinones, catechols,aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives,reductones and phenylenediamines. Combinations of developing agents canbe employed in the practice of this invention. The developing agents canbe in a silver halide emulsion and/or in another suitable location inthe photographic element. The developing agents may be added fromsuitable solvents or in the form of dispersions as described in YackelU.S. Pat. No. 2,592,368 issued Apr. 8, 1952 and Dunn et a1. French Pat.No. 1,505,778.

The processing solutions of this invention may be used in thedevelopment of elements designed for colloid transfer processes such asdescribed in Yutzy et al. U.S. Pat. No. 2,716,059 issued Aug. 23, 1955,silver salt diffusion transfer processes such as described in Rott U.S.Pat. No. 2,352,014 issued June 20, 1944, and Land U.S. Pat. No.2,543,181 issued Feb. 27, 1951, Yackel at al. U.S. Pat. No. 3,020,155issued Feb. 6, 1962, and Land U.S. Pat. No. 2,861,885 issued Nov. 25,1958; color image transfer processes such as described in Rogers US.Pat. Nos. 3,087,817 issued Apr. 30, 1963; 3,185,567 issued May 25, 1965;and 2,983,606 issuedMay 9, 1961; Weyerts et al. U.S. Pat. No. 3,253,915issued May 31, 1966; Whitmore et al. U.S. Pat. No. 3,227,550 issued Jan.4, 1966; Barr et al. U.S. Pat. No. 3,227,551 issued Jan. 4, 1966,Whitmore U.S. Pat. No. 3,227,552 issued Jan. 4, 1966; and Land U.S. Pat.Nos. 3,415,644; 3,415,645; 3,415,646 issued Dec. 10, 1968; andimbibition transfer processes as de' scribed in Minsk U.S. Pat. No.2,882,156 issued Apr. 14, 1959.

The processing solutions of this invention can be used with elementsdesigned for color photography, for example, elements containingcolor-forming couplers such as those described in Frohlich et al. U.S.Pat. No. 2,376,679 issued May 22, 1945, Jelley et al. U.S. Pat. No.2,322,027 issued June 15, 1943; Fierke et al. U.S. Pat. No. 2,801,171issued July 30, 1957, Godowsky U.S. Pat. No. 2,698,794 issued Jan. 4,1966, Barr et al. U.S. Pat. No. 3,227,554 issued Jan. 4, 1966, andGraham et al. U.S. Pat. No. 3,046,129 issued July 24, 1962; or elementsto be developed in solutions containing color-forming couplers such asthose described in Mannes et al. U.S. Pat. No. 2,252,718 issued Aug. 19,1941,Carroll et al. U.S. Pat. No. 2,592,243 issued Apr. 8, 1952; andSchwan et al. U.S. Pat. No. 2,950,970 issued Aug. 30, 1960; and infalse-sensitized color materials such as those described in Hanson U.S.Pat. No. 2,763,549 issued Sept. 18, 1956.

The exposed silver halide emulsion can be either tray processed ormachine processed in the presence of the processing solutions of thisinvention. In a preferred method a photographic element :is machineprocessed whereby the element is processed in one continuous motion bytransporting it into and out of at least one processing solution in themanner shown, for example, by U.S. Pat. Nos. 3,025,779 of Russell andKunz issued Mar. 20, 1962; 3,078,024 of Sardeson issued Feb. 19, 1963;3,122,086 of Fitch issued Feb. 25, 1964; 3,149,551 of Cramer issuedSept. 22, 1964; 3,156,173 of Meyer issued Nov. 10, 1964; and 3,224,356of Fleisher and Hixon issued Feb. 2.1, 1965.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

I claim:

1. A photographic developing composition comprising water, a silverhalide developing agent and reaction products of a thioamine which iscysteine, cystine, DL- penicillamine, DL-homocysteinethiolactone or2-aminoethanethiol with glutaraldehyde or with glutaraldehyde bisulfitein which said reaction products are obtained by reacting a mixturehaving a molar ratio of from about 4 to l to about 1 to 60 of saidthioamine to glutaraldehyde or glutaraldehyde bisulfite.

2. A photographic developing composition of claim 1, in which saidcomposition contains reaction products of cysteine and glutaraldehyde.

3. A photographic developing composition of claim 1 in which saidreaction products are obtained by reacting a mixture having a molarratio of from about 2 to l to about 1 to 8 of the said thioamine toglutaraldehyde.

4. A photographic developing composition of claim 1 in which saidreaction products are obtained by reacting a mixture having a l to 1molar ratio of said thioamine to said glutaraldehyde.

5. A photographic developing composition comprising water, a silverhalide developing agent and reaction products of cysteine, withglutaraldehyde or with glutaraldehyde bisulfite in which said reactionproducts are obtained by reacting a mixture having a molar ratio of fromabout 4 to l to about 1 to 60 of said cysteine to glutaraldehyde orglutaraldehyde bisulfite.

6. A method of developing an exposed photographic silver halide elementwhich comprises treating an exposed silver halide layer with aphotographic developing solution comprising water, a silver halidedeveloping agent and reaction products of a thioamine which is cysteine,cystine, DL-penicillamine, DL-homocysteinethiolactone or2-aminoethanethiol with glutaraldehyde or with glutaraldehyde bisulfitein which said reaction products are obtained by reacting a mixturehaving a molar ratio of from about 4 to l to about I to 60 of saidthioamine to said glutaraldehyde or glutaraldehyde bisulfite.

7. A method of claim 6 in which said reaction products are of cysteineand glutaraldehyde.

8. A method of claim 6 in which said reaction products are obtained byreacting a mixture having about 4 to l to about 1 to 60 of saidthioamine to glutaraldehyde.

9. A method of claim 6 in which said reaction products are obtained byreacting a mixture having a molar ratio of from about 2 to 1 to about 1to 8 of said thioamine to glutaraldehyde.

10. A method of claim 6 in which said reaction products are obtained byreacting a misture having a l to 1 molar ratio of said thioamine to saidglutaraldehyde.

1. A PHOTOGRAPHIC DEVELOPING COMPOSITION COMPRISING WATER, A SILVER HALIDE DEVELOPING AGENT AND REACTION PRODUCTS OF A THIOAMINE WHICH IS CYSTEINE, CYSTINE, DL-PENICILLAMINE DL-HOMOCYSTEINETHIOLACTONER OR 2-AMINOETHANETHIOL WITH GLUTARALDEHYDE OR WITH GLUTARALDEHYDE BISULFITE IN WHICH SAID REACTION PRODUCTS ARE OBTAINED BY REACTING A MIXTURE HAVING A MOLAR RATIO OF FROM ABOUT 4 TO 1 TO ABOUT 1 TO 60 OF SAID THIOAMINE TO GLUTARALDEHYDE OR GULTARALDEHYDE BISUFITE.
 2. A photographic developing composition of claim 1, in which said composition contains reaction products of cysteine and glutaraldehyde.
 3. A photographic developing composition of claim 1 in which said reaction products are obtained by reacting a mixture having a molar ratio of from about 2 to 1 to about 1 to 8 of the said thioamine to glutaraldehyde.
 4. A photographic developing composition of claim 1 in which said reaction products are obtained by reacting a mixture having a 1 to 1 molar ratio of said thioamine to said glutaraldehyde.
 5. A photographic developing composition comprising water, a silver halide developing agent and reaction products of cysteine, with glutaraldehyde or with glutaraldehyde bisulfite in which said reaction products are obtained by reacting a mixture having a molar ratio of from about 4 to 1 to about 1 to 60 of said cysteine to glutaraldehyde or glutaraldehyde bisulfite.
 6. A method of developing an exposed photographic silver halide element which comprises treating an exposed silver halide layer with a photographic developing solution comprising water, a silver halide developing agent and reaction products of a thioamine which is cysteine, cystine, DL-penicillamine, DL-homocysteinethiolactone or 2-aminoethanethiol with glutaraldehyde or with glutaraldehyde bisulfite in which said reaction products are obtained by reacting a mixture having a molar ratio of from about 4 to 1 to about 1 to 60 of said thioamine to said glutaraldehyde or glutaraldehyde bisulfite.
 7. A method of claim 6 in which said reaction products are of cysteine and glutaraldehyde.
 8. A method of claim 6 in which said reaction products are obtained by reacting a mixture having about 4 to 1 to about 1 to 60 of said thioamine to glutaraldehyde.
 9. A method of claim 6 in which said reaction products are obtained by reacting a mixture having a molar ratio of from about 2 to 1 to about 1 to 8 of said thioamine to glutaraldehyde.
 10. A method of claim 6 in which said reaction products are obtained by reacting a misture having a 1 to 1 molar ratio of said thioamine to said glutaraldehyde. 